CN101525748B - Clean rare-earth salt passive film - Google Patents
Clean rare-earth salt passive film Download PDFInfo
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- CN101525748B CN101525748B CN2009100943692A CN200910094369A CN101525748B CN 101525748 B CN101525748 B CN 101525748B CN 2009100943692 A CN2009100943692 A CN 2009100943692A CN 200910094369 A CN200910094369 A CN 200910094369A CN 101525748 B CN101525748 B CN 101525748B
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- zinc
- rare
- iron alloy
- passive film
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 34
- -1 rare-earth salt Chemical class 0.000 title claims abstract description 34
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 38
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002161 passivation Methods 0.000 claims abstract description 26
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 18
- 239000010959 steel Substances 0.000 claims abstract description 18
- 238000005246 galvanizing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 239000008399 tap water Substances 0.000 claims description 6
- 235000020679 tap water Nutrition 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000007540 photo-reduction reaction Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 abstract description 2
- 229910002567 K2S2O8 Inorganic materials 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 235000019394 potassium persulphate Nutrition 0.000 abstract 1
- 235000019795 sodium metasilicate Nutrition 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a clean rare-earth salt passive film, mainly used for post treatment procedure of galvanizing or zinc-iron alloy of steel parts, belonging to the technical field of metal material surface treatment. A bright dipping solution composed of 2-5ml of HNO3 and H2O as well as a passivation solution composed of 15-30g/L of cerous nitrate or cerium chloride, 2-5g/L of K2S2O8, 2-6g/L of Na2SiO3, 2-6g/L of H2BO3, 5-20ml/L of H2O2, 5-15ml/L of HCl and the balance being H2O are prepared, diluted HCl or NaOH solution is used for adjusting the pH value to 1.8-2.8, then the steel parts of the galvanizing or zinc-iron alloy is taken out, washed and then placed in the bright dipping solution for 3-10 seconds, washed by running water and then placed in the passivation solution for passivation of 30-90 seconds at room temperature, and taken out, washed by running water and dried by an air blower. The corrosion resistance of the steel parts of the galvanizing or zinc-iron alloy processed by the passivation technique is remarkably improved, and the passivation technique has the advantages of toxic substance-free, high stability and reliability, excellent product performance, belongs to clean and environment-friendly, economic and practical chromium-free passivation technique and has significant social meaning and application value.
Description
Technical field
The present invention relates to belong to the steel material surface processing technology field, particularly relate to the preparation of clean rare-earth salt passive film, be used for the postprocessing working procedures of iron and steel parts electro-galvanizing or zinc-iron alloy.
Background technology
Corrosion and corrosion protection is related to Economic development and people's life safety, and surface engineering technology is to solve component of machine and material corrosion and most economical effective means of protection and method.
Zinc-plated and zinc-iron alloy is the effective way that improves the steel-iron components resistance to corrosion, is widely used at present in many fields such as shipbuilding industry, mechanical industry, aviation, building.But in a humid environment, especially in hygrothermal environment, zinc-plated and zinc-iron alloy layer easily corrodes, and makes coating surface form corrosion product---the white rust of lead or white loose; Time has been grown and red rust can occur, thereby loses preservative effect.In order to improve the solidity to corrosion of coating, must behind iron and steel parts electro-galvanizing or zinc-iron alloy, carry out Passivation Treatment to coating, form fine and close passive film on the surface of electrolytic coating, thereby improve the solidity to corrosion of component.
Present nearly all steel plate galvanized aftertreatment all is to generate chromate passivation film at galvanized steel sheet surface, but owing to sexavalent chrome toxicity in the chromic salt is high and easily carcinogenic, government's strictness limits using and discharging of chromic salt; And emphasize in the Eleventh Five-Year Plan that a development environment resist technology gives priority to.Therefore chromate passivation film is faced with severe challenge, and seeks and adopt the chromium-free deactivation film of compliance with environmental protection requirements just becoming the inexorable trend of present development.Chromium-free deactivation film on the at present both at home and abroad zinc-plated and alloy layer mainly contains molybdate passive film, rare-earth salts passive film, silicate passive film, phytic acid passive film and organism passive film etc., but the solidity to corrosion that the passivation effect of these chromium-free deactivation films does not also reach chromate passivation film to be had, or expense is too high, to such an extent as to also there is not a kind of chromium-free deactivation film to replace chromate passivation film fully at present.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing passive film, provide a kind of do not contain Toxic matter, electro-galvanizing that the product performance of handling are good, production cost is low and zinc-iron alloy clean rare-earth salt passive film.
Technical scheme of the present invention is: the preparation process of this clean rare-earth salt passive film is: electro-galvanizing or zinc-iron alloy → washing → bright dipping → washing → passivation → and wash → dry up.
Go out being operating as of photoreduction process: the component that will be coated with zinc or zinc-iron alloy are put into by HNO
3And H
2In the light-emitting solution that O forms, stopped under the room temperature 3～10 seconds, take out then and be coated with zinc or zinc-iron alloy component.Each constituent and content thereof are in the light-emitting solution: HNO
32～5ml/L, all the other are H
2O.
Being operating as of passivating process: the component that are coated with zinc or zinc-iron alloy after the bright dipping are put into by rare-earth salts, K
2S
2O
8, Na
2SiO
3, H
3BO
3, H
2O
2, HCl and H
2After in the rare-earth salt passivation liquid that O forms, the pH of control passivating solution is 1.8～2.8, stops under the room temperature 30～90 seconds, takes out zinc-plated then or the zinc-iron alloy component.Each constituent and content thereof are in the passivating solution: rare-earth salts 15～30g/L, K
2S
2O
82～5g/L, Na
2SiO
3.3H
2O 2～6g/L, H
3BO
32～6g/L, H
2O
25～20ml/L, HCl 5～15ml/L, all the other are H
2O.Rare-earth salts can be any in cerous nitrate or the cerous chlorate.
Each constituent content and operational condition can be selected in given range according to actual needs in light-emitting solution and the passivating solution.
Being operating as of water washing process: component that are coated with zinc or zinc-iron alloy that will just plate or the component that are coated with zinc or zinc-iron alloy after the bright dipping or the component that are coated with zinc or zinc-iron alloy after the passivation wash repeatedly with tap water, till the component surface that is coated with zinc or zinc-iron alloy cleans up.
Dry up being operating as of process: with the component that are coated with zinc or zinc-iron alloy after passivation and the washing with till blowing the moisture of water machine and drying up with component surface.
The present invention is owing to adopt the main component of rare-earth salts as passivating solution, and is equipped with K
2S
2O
8, Na
2SiO
3, H
3BO
3, H
2O
2, HCl, be used for the aftertreatment of electro-galvanizing and zinc-iron alloy technology, can go out clean rare-earth salt passive film at electro-galvanizing and zinc-iron alloy surface preparation, can significantly improve the solidity to corrosion of electro-galvanizing and zinc-iron alloy, make salt-fog test go out the white rust time and can reach more than 25～50 hours.Owing in passive film, do not contain chromium, overcome chromate passivation film toxicity greatly, shortcoming such as not environmental protection, can realize the cleaner production of electro-galvanizing and zinc-iron alloy.This clean rare-earth salt passive film is reliable and stable, and excellent property can replace chromate passivation film, has very great social significance and using value.
Description of drawings
Fig. 1 is clean rare-earth salt passive film preparation flow figure of the present invention.
Embodiment
Further specify flesh and blood of the present invention below in conjunction with example, but content of the present invention is not limited to this.
Embodiment 1: local galvanized surface of steel plate is prepared clean rare-earth salt passive film.
After the pre-treatments such as this steel plate eliminated rust before electroplating, oil removing, activation, put into electroplate liquid to electroplate, the plating bath of zincincation is formed and operational condition is: ZnCl
280g/L, KCl 200g/L, additive pH value an amount of, plating bath remain on about 5.5, and current density is 1.2A/dm
2, temperature is a room temperature, electroplating time is 25 minutes.
Preparation is by HNO
32ml/L and H
2The light-emitting solution that O forms and by cerous chlorate 15g/L, K
2S
2O
82g/L, Na
2SiO
32g/L, H
3BO
32g/L, H
2O
25ml/L, HCl 5ml/L and H
2The passivating solution that O forms, with rare HCl or NaOH solution the pH value is transferred to 2.8, steel plate after will electroplating then takes out, after cleaning, put into light-emitting solution earlier and stopped 10 seconds, take out, put into passivating solution again with the tap water flushing, passivation is 90 seconds under the room temperature, take out this steel plate galvanized then, after tap water cleans up, dry up, prepare clean rare-earth salt passive film at surface of steel plate with blower.
This rare-earth salt passive film outward appearance is light evenly, goes out the white rust time above 25 hours through neutral salt spray test.
Embodiment 2: the surface of steel plate of parcel plating zn-fe alloy is prepared clean rare-earth salt passive film
Before carrying out passivation, steel plate is implemented to electroplate after pre-treatment (rust cleaning, oil removing, activation), and the plating bath of zinc-iron alloy plating process is formed and operational condition is: ZnCl
2100g/L, KCl 230g/L, FeSO
47H
2O 10g/L, xitix 1.2g/L, additive are an amount of, pH value 4.0, cathode current density 1.8A/dm
2, temperature is room temperature, electroplating time is 40 minutes, iron level is 0.5% in the gained Zn-Fe alloy coating.
Preparation is by HNO
33ml/L and H
2The light-emitting solution that O forms and by cerous nitrate 25g/L, K
2S
2O
84g/L, Na
2SiO
33g/L, H
3BO
33g/L, H
2O
210ml/L, HCl 10ml/L and H
2The passivating solution that O forms, with rare HCl or NaOH solution the pH value is transferred to 2.4, steel plate after will electroplating then takes out, after cleaning, put into light-emitting solution earlier and stopped 6 seconds, take out, put into passivating solution again with the tap water flushing, passivation is 60 seconds under the room temperature, take out this steel pipe then, after tap water cleans up, dry up, prepare clean rare-earth salt passive film at the surface of steel plate of electroplating zn-fe alloy with blower.。
This rare-earth salt passive film outward appearance is light evenly, goes out the white rust time above 50 hours through neutral salt spray test, has not only surpassed existing chromate passivation film corrosion resisting property (25 hours), but also has surpassed national standard (30 hours).
Claims (6)
1. clean rare-earth salt passive film, it is characterized in that going out clean rare-earth salt passive film at iron and steel parts electro-galvanizing or zinc-iron alloy surface preparation, this passive film forms fine and close rare-earth salt passive film on the surface of zinc or Zn-Fe alloy electroplating layer, this clean rare-earth salt passive film preparation flow is: electro-galvanizing or zinc-iron alloy → washing → bright dipping → washing → passivation → and wash → dry up;
Being operating as of passivating process: the component that are coated with zinc or zinc-iron alloy after the bright dipping are put into by rare-earth salts, K
2S
2O
8, Na
2SiO
3.3H
2O, H
3BO
3, H
2O
2, HCl and H
2After in the rare-earth salt passivation liquid that O forms, stopped under the room temperature 30～90 seconds, take out zinc-plated then or the zinc-iron alloy component;
Each constituent and content thereof are in the passivating solution: rare-earth salts 15～30g/L, K
2S
2O
82～5g/L, Na
2SiO
3.3H
2O 2～6g/L, H
3BO
32～6g/L, H
2O
25～20ml/L, HCl 5～15ml/L, all the other are H
2O treats that the each component dissolving transfers to 1.8～2.8 with rare HCl or NaOH solution with the pH value in the back fully in the passivating solution.
2. clean rare-earth salt passive film according to claim 1, it is characterized in that described being operating as of photoreduction process that go out: the component that will be coated with zinc or zinc-iron alloy are put into by HNO
3And H
2In the light-emitting solution that O forms, stopped under the room temperature 3～10 seconds, take out then and be coated with zinc or zinc-iron alloy component.
3. clean rare-earth salt passive film according to claim 2 is characterized in that in the light-emitting solution that each constituent and content thereof are: HNO
32～5ml/L, all the other are H
2O.
4. clean rare-earth salt passive film according to claim 1 is characterized in that rare-earth salts is any in cerous nitrate or the cerous chlorate.
5. clean rare-earth salt passive film according to claim 1, it is characterized in that being operating as of water washing process: component that are coated with zinc or zinc-iron alloy that will just plate or the component that are coated with zinc or zinc-iron alloy after the bright dipping or the component that are coated with zinc or zinc-iron alloy after the passivation wash repeatedly with tap water, till the component surface that is coated with zinc or zinc-iron alloy cleans up.
6. clean rare-earth salt passive film according to claim 1 is characterized in that being operating as of the process that dries up: with the component that are coated with zinc or zinc-iron alloy after passivation and the washing with till blowing the moisture of water machine and drying up with component surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100943692A CN101525748B (en) | 2009-04-17 | 2009-04-17 | Clean rare-earth salt passive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100943692A CN101525748B (en) | 2009-04-17 | 2009-04-17 | Clean rare-earth salt passive film |
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| Publication Number | Publication Date |
|---|---|
| CN101525748A CN101525748A (en) | 2009-09-09 |
| CN101525748B true CN101525748B (en) | 2011-04-20 |
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ID=41093816
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|---|---|---|---|
| CN2009100943692A Expired - Fee Related CN101525748B (en) | 2009-04-17 | 2009-04-17 | Clean rare-earth salt passive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107393820B (en) * | 2017-06-05 | 2019-12-13 | 长安大学 | surface passivation solution and application thereof in surface passivation of cadmium manganese telluride crystals |
| CN108103487A (en) * | 2017-12-18 | 2018-06-01 | 陕西省石油化工研究设计院 | A kind of zinc-plated silicate passivation solution and preparation method thereof |
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2009
- 2009-04-17 CN CN2009100943692A patent/CN101525748B/en not_active Expired - Fee Related
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